1.

In calibrating a 10-mL pipet, a measured volume of water was transferred to a tared flask and
weighed, yielding a mass of 9.9814 g. (a) Calculate, with and without correcting for buoyancy,
the volume of water delivered by the pipet. Assume that the density of water is 0.99707 g/cm3
and that the density of the weights is 8.40 g/cm3. (b) What are the absolute and relative errors
introduced by failing to account for the effect of buoyancy? Is this a significant source of
determinate error for the calibration of a pipet? Explain.
2. A 10.00-g sample containing an analyte was transferred to a 250-mL volumetric flask and diluted
to volume. When a 10.00-mL aliquot of the resulting solution was diluted to 25.00 mL it was
found to give a signal of 0.235 (arbitrary units). A second 10.00-mL aliquot was spiked with 10.00
mL of a 1.00- ppm standard solution of the analyte and diluted to 25.00 mL. The signal for the
spiked sample was found to be 0.502. Calculate the weight percent of analyte in the original
sample.
3. A standard sample was prepared containing 10.0 ppm of an analyte and 15.0 ppm of an internal
standard. Analysis of the sample gave signals for the analyte and internal standard of 0.155 and
0.233 (arbitrary units), respectively. Sufficient internal standard was added to a sample to make
it 15.0 ppm in the internal standard. Analysis of the sample yielded signals for the analyte and
internal standard of 0.274 and 0.198, respectively. Report the concentration of analyte in the
sample.
4. The following standardization data were provided for a series of external standards of Cd2+ that
had been buffered to a pH of 4.6.14
[Cd2+] (nM) 15.4 30.4 44.9 59.0 72.7 86.0
Smeas (nA) 4.8 11.4 18.2 26.6 32.3 37.7
(a) Determine the standardization relationship by a linear regression analysis, and report the
confidence intervals for the slope and y-intercept. (b) Construct a plot of the residuals, and
comment on their significance. At a pH of 3.7 the following data were recorded
[Cd2+] (nM) 15.4 30.4 44.9 59.0 72.7 86.0
Smeas (nA) 15.0 42.7 58.5 77.0 101 118
(c) How much more or less sensitive is this method at the lower pH? (d) A single sample is
buffered to a pH of 3.7 and analyzed for cadmium, yielding a signal of 66.3. Report the
concentration of Cd2+ in the sample and its 95% confidence interval.
5. To determine the concentration of analyte in a sample, a standard additions was performed. A
5.00-mL portion of the sample was analyzed and then successive 0.10-mL spikes of a 600.0-ppb
standard of the analyte were added, analyzing after each spike. The following results were
obtained

Volume of Spike(mL) Signal (arbitrary units)

0.00 0.119
0.10 0.231
0.20 0.339
0.30 0.442
Construct an appropriate standard additions calibration curve, and use a linear regression
analysis to determine the concentration of analyte in the original sample and its 95%
confidence interval.
 x y xi xiyi i (yi-i)
15.4 4.8 237.16 73.92 4.65774 0.020238
30.4 11.4 924.16 346.56 11.81424 0.171595
44.9 18.2 2016.01 817.18 18.73219 0.283226
59 26.6 3481 1569.4 25.4593 1.301196
72.7 32.3 5285.29 2348.21 31.99557 0.092678
86 37.7 7396 3242.2 38.341 0.410881
= 308.4 131 19339.62 8397.47 2.279814
 pH 4,6
140
118
120
101
y = 0.4771 [Cd2+] - 2.68960
100
77
80
Smeas

58.5
60
42.7
40
15
20

0
0 10 20 30 40 50 60 70 80 90 100
konsentrasi

x y xi xiyi i (yi-i)
15.4 15 237.16 231 17.06788 4.276128
30.4 42.7 924.16 1298.08 38.58088 16.96715
44.9 58.5 2016.01 2626.65 59.37678 0.768743
59 77 3481 4543 79.599 6.754801
72.7 101 5285.29 7342.7 99.24754 3.071116
86 118 7396 10148 118.3224 0.103942
= 308.4 412.2 19339.62 26189.43 31.94188

pH 3,7
140
120 y = 1.4342x - 5.0188
100
Smeas

80
60
40
20
0
0 20 40 60 80 100

konsentrasi
 (Vs) (Vf) (Signal)y i (yi-i) Cs(Vs/Vf)
0 5 0.119 0.1191 1E-08 0
0.1 5.1 0.231 0.230865 1.83045E-08 11.7647059
0.2 5.2 0.339 0.338331 4.4787E-07 23.0769231
0.3 5.3 0.442 0.441742 6.68174E-08 33.9622642
= 0.6 1.131 1.130037 5.42992E-07 68.8038931

0.5
0.442
0.45 y = 0.0095x + 0.1191
0.4
0.339
0.35
0.3
Signal

0.231
0.25
0.2
0.150.119
0.1
0.05
0
0 5 10 15 20 25 30 35 40
Cs(Vs/Vf